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Method for direct conversion of aromatic alkyne into chiral alcohol through one-pot process

A technology for conversion into and chiral alcohols, applied in organic chemistry methods, chemical instruments and methods, preparation of organic compounds, etc., can solve the problems of complex synthesis of ketones and organometallic reagents, difficult to obtain, etc., and achieves easy operation and reaction conditions. Mild, enantioselective effect

Active Publication Date: 2018-06-01
CHINA THREE GORGES UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] Chiral alcohols are usually prepared by the asymmetric reduction of ketones or the asymmetric addition reaction of ketones with organometallic reagents, but some ketones and organometallic reagents are complex and difficult to obtain

Method used

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  • Method for direct conversion of aromatic alkyne into chiral alcohol through one-pot process
  • Method for direct conversion of aromatic alkyne into chiral alcohol through one-pot process
  • Method for direct conversion of aromatic alkyne into chiral alcohol through one-pot process

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Embodiment 1: the asymmetric synthesis of (S)-1-phenylethanol

[0033]

[0034] Add 0.5 mmol of phenylacetylene to the test tube, followed by adding CF 3 SO 3 H (20mol%, 9uL), H 2 O(2equiv., 20 uL), CF 3 CH 2 OH (1mL), after reacting at 40°C for 4h, add 0.005mmol catalyst A, HCOONa (0.5mmol, 34mg, 2.5mmol, 170mg), H 2 O (1 mL), react at 50°C for 5 hours. After the reaction was finished, it was extracted 3 times with ethyl acetate, and the combined organic phases were concentrated to dryness. The separation yield: 93% (petroleum ether: ethyl acetate=5:1), and the ee of the product (S)-1-phenylethanol was determined by HPLC. The value is 97%. HPLC separation conditions: chiral column Daicel OD-H-H column, mobile phase: n-hexane / isopropanol=97:3 (volume ratio), flow rate: 1.0 ml / min, wavelength: 254 nm, column temperature: 30 degrees Celsius, t 1 = 11.58 minutes, t 2 = 13.82 minutes; 1 H NMR (400MHz, CDCl 3 ):δ=7.43-7.37(m,4H),7.34-7.30(m,1H),4.93(dd,J 1 =12...

Embodiment 2

[0035] Embodiment 2: the asymmetric synthesis of (S)-1-phenylethanol

[0036]

[0037] Add 0.5 mmol of phenylacetylene to the test tube, followed by adding CF 3 SO 3 H (20mol%, 9uL), H 2 O(2equiv., 20 uL), CF 3 CH 2 OH (1mL), after reacting at 40°C for 4h, add 0.005mmol catalyst B, HCOONa (0.5mmol, 34 mg), H 2O (1 mL), react at 50°C for 5 hours. After the reaction was finished, it was extracted 3 times with ethyl acetate, and the combined organic phases were concentrated to dryness. The isolated yield: 41% (petroleum ether: ethyl acetate=5:1), and the ee of the product (S)-1-phenylethanol was determined by HPLC. The value is 93%.

Embodiment 3

[0038] Embodiment 3: the asymmetric synthesis of (S)-1-phenylethanol

[0039]

[0040] Add 0.5 mmol of phenylacetylene to the test tube, followed by adding CF 3 SO 3 H (20mol%, 9uL), H 2 O(2equiv., 20 uL), CF 3 CH 2 OH (1mL), after reacting at 40°C for 4h, add 0.005mmol catalyst D, HCOONa (0.5mmol, 34 mg), H 2 O (1 mL), react at 50°C for 5 hours. After the reaction was finished, it was extracted 3 times with ethyl acetate, and the combined organic phases were concentrated to dryness. The isolated yield: 68% (petroleum ether: ethyl acetate=5:1), and the ee of the product (S)-1-phenylethanol was determined by HPLC. value of 95%.

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Abstract

The invention relates to a method for direct conversion of aromatic alkyne into chiral alcohol through a one-pot process. The method uses cheap and easily-available alkyne I as a raw material, adoptsa two-step one-pot strategy for direct synthesis of chiral alcohol II, and comprises the following concrete steps: step 1) with fluorine-containing alcohol and water as solvents, allowing the alkyne Ito generate a hydration reaction under the catalysis of trifluoromethanesulfonic acid so as to generate an intermediate namely ketone; and step 2) directly adding a complex of monossulfonyl chiral diamine and metal ruthenium or rhodium or iridium as a catalyst into a reaction system, and with a mixture of a sodium formate aqueous solution or formic acid-triethylamine as a hydrogen source, carrying out an asymmetric transfer hydrogenation reaction so as to obtain a product II. The method provided by the invention has the following advantages: operation is simple and convenient; reaction conditions are mild; and a substrate has wide application range and high enantioselectivity. Concretely, the method provided by the invention has a general reaction formula which is described in the specification.

Description

technical field [0001] The invention belongs to the technical field of asymmetric catalysis, and in particular relates to a method for directly converting aromatic alkynes into chiral alcohols in one pot. Background technique [0002] Chiral alcohols are usually prepared by asymmetric reduction of ketones or asymmetric addition of ketones with organometallic reagents, but some ketones and organometallic reagents are complex to synthesize and not easy to obtain. Alkynes are a kind of cheap and easy-to-obtain raw materials. Starting from alkynes, the method of directly synthesizing chiral alcohols using the strategy of "hydration reaction-asymmetric reduction two-step one-pot method" has atom economy and step economy, which is in line with green chemistry. The principle has important application prospects. Direct conversion of alkynes to chiral alcohols using this strategy has been reported, but requires the use of a bimetallic catalytic system, such as: (IPr)AuBF 4 ] / Ru-TsD...

Claims

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Application Information

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IPC IPC(8): C07C29/143C07C33/22C07C33/20C07C33/46C07C33/18C07C41/26C07C43/23C07C201/12C07C205/19B01J31/22
CPCC07C29/143C07C41/26C07C45/26C07C201/12B01J31/2295B01J2531/0225B01J2531/0238B01J2531/821B01J2531/822B01J2531/827C07B2200/07C07C49/78C07C49/84C07C49/807C07C205/45C07C33/22C07C33/20C07C33/46C07C33/18C07C43/23C07C205/19
Inventor 周海峰刘欢刘森生刘祈星
Owner CHINA THREE GORGES UNIV
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